CN102066000A - Catalyst for producing acrylic acid and method for producing acrylic acid using the catalyst - Google Patents
Catalyst for producing acrylic acid and method for producing acrylic acid using the catalyst Download PDFInfo
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- CN102066000A CN102066000A CN2009801231284A CN200980123128A CN102066000A CN 102066000 A CN102066000 A CN 102066000A CN 2009801231284 A CN2009801231284 A CN 2009801231284A CN 200980123128 A CN200980123128 A CN 200980123128A CN 102066000 A CN102066000 A CN 102066000A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/28—Molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The catalyst of the present invention is a catalyst for producing acrylic acid by catalytic gas phase oxidation of propane and/or acrolein with a molecular oxygen-containing gas, the catalyst containing a catalytically active component containing molybdenum and vanadium as essential components, and having a crystallinity T in the range of 5% to 20% when measured by X-ray diffraction analysis using Cu — K α rays, the crystallinity T being in the range of 5 ° to 90 °. The method for producing acrylic acid of the present invention is a method for producing acrylic acid by gas-phase catalytic oxidation of propane and/or acrolein with a molecular oxygen-containing gas, and is characterized by comprising a step of gas-phase catalytic oxidation in the presence of the catalyst. According to the catalyst and the method for producing acrylic acid of the present invention, acrylic acid can be produced stably for a long period of time with high yield.
Description
Technical field
The present invention utilizes molecular oxygen that propane and/or methacrylaldehyde are carried out the method for producing acrylic acid that catalytic gas phase oxidation prepares acrylic acid catalyst and used this catalyst about being used to.
Background technology
Acrylic acid as the raw material of various synthetic resin, coating, plasticizer industrial very important, in recent years as its importance of raw material of water-absorbing resins also in continuous lifting.As method for producing acrylic acid, the most general have 2 sections following oxidizing process: the catalytic gas phase oxidation by propylene obtains methacrylaldehyde, and the catalytic gas phase oxidation by the methacrylaldehyde that makes obtains acrylic acid again.
On the other hand, because the price variance of propane and propylene, propane is carried out 1 section oxidation obtain acrylic acid and also obtain exploitation in recent years, have various suggestions to propose.Preparing acrylic acid catalyst as being used to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation, is that the center is inquired into molybdenum-vanadium, and each company is that purpose has proposed various suggestions to improve catalyst performance.
Prepare in acrylic acid reaction in gaseous oxidation, have that also spendable catalyst is proposed under various high activities, acrylic acid yield height and the high-load condition by methacrylaldehyde.For example, put down in writing following catalyst in the patent documentation 1: this catalyst belongs to VMo when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure
3O
11The peak and belong to V
2O
5The ratio of peak intensity at peak be positioned at particular range.Put down in writing following catalyst in the patent documentation 2: in having used the Alpha-ray X-ray diffraction analysis of Cu-K, the specific peak of this catalyst is maximum.Put down in writing following catalyst in the patent documentation 3: in having used the Alpha-ray X-ray diffraction analysis of Cu-K, this catalyst has specific peak in 2 θ are 5 °～50 ° scope.In addition, prepare acrylic acid catalyst as the gaseous oxidation that is used for by propane, put down in writing following catalyst in the patent documentation 4: in X-ray diffraction analysis, there is the peak that shows maximum intensity in this catalyst at specific angle of reflection place, and perhaps there is not the peak in this catalyst at specific angle of reflection place.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-233757 communique
Patent documentation 2: Japanese kokai publication hei 8-299797 communique
Patent documentation 3: Japanese kokai publication hei 9-194213 communique
Patent documentation 4: Japanese Unexamined Patent Application Publication 2004-504288 communique
Summary of the invention
Invent technical problem to be solved
Acrylic acid now in the whole world scale with millions of ton/years produce, it needs further to increase as the raw material of water-absorbing resins.Consider the surging of cost of material in recent years,, also have very significant meaning economically even acrylic acid yield improves 0.1% on commercial scale.Though the catalyst of record all can seen some improvement aspect the catalyst performances such as acrylic acid yield and service life in the patent documentation 1～4, also has room for improvement from commercial scale.
Use the catalyst of record in the patent documentation 1, though in the initial reaction stage acrylic acid yield than higher, even but be under the 4.5% lower condition at the raw material propylene aldehyde concentration, in successive reaction after 8000 hours, acrylic acid yield drops to 92.9 moles of % from 94.4 moles of % in when beginning reaction, and is therefore also insufficient from the catalyst life this point.Though put down in writing really very high acrylic acid yield in patent documentation 2, it just mostly is most the result that the laboratory level evaluation of 30ml obtains at catalytic amount.And, do not estimate about this life of catalyst.In patent documentation 3, though than higher, it is the same with above-mentioned patent documentation 1 in initial reaction stage acrylic acid selection rate, be to be the evaluation of carrying out under the 5.0% lower condition at the raw material propylene aldehyde concentration, and be the performance of initial reaction stage fully, and do not estimate about life of catalyst.Carrying out aspect catalyst performance, also leaving query under the acrylic acid situation of long-time prepared in reaction continuously.In patent documentation 4, though showed that as the gas-phase oxidization process of propane than higher acrylic acid yield, it is the performance of initial reaction stage fully, and does not estimate about life of catalyst.Carrying out aspect catalyst performance, also leaving query under the acrylic acid situation of long-time prepared in reaction continuously.In addition, in patent documentation 1～4, be not controlled at any record that improves this technological thought of acrylic acid yield in the proper range for a long time about degree of crystallinity with the catalyst activity composition.
The present invention is on the basis of using for reference above-mentioned situation and the invention of doing, its purpose is, when preparing acrylic acid, provide a kind of have catalyst performance such as outstanding catalyst activity, selectivity and outstanding catalyst life, and the long-term catalyst of showing stability from propane and/or methacrylaldehyde.
The means that are used for the technical solution problem
The catalyst of the present invention that can solve the problems of the technologies described above is a kind ofly to be used to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation to prepare acrylic acid catalyst, it is characterized in that, it is the catalyst activity composition of necessary composition that described catalyst contains with molybdenum and vanadium, when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the catalyst activity composition more than 2 θ=5 ° the degree of crystallinity T in 90 ° of following scopes in 20% following scope more than 5%.By having the degree of crystallinity T of above-mentioned scope, catalyst of the present invention has had catalyst performance and outstanding catalyst lifes such as outstanding catalyst activity, selectivity, and has stability for a long time.
Catalyst of the present invention is more preferably: as shown in the formula shown in (1) like that, when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the degree of crystallinity ratio R that is calculated with respect to the ratio of above-mentioned degree of crystallinity T at the degree of crystallinity M at ° peak value place, 2 θ=22.2 ± 0.5 by the catalyst activity composition is in 0.30 following scope more than 0.06.Except degree of crystallinity T, also by degree of crystallinity ratio R is adjusted in the above-mentioned scope, just can easily obtain having more outstanding catalyst performance and catalyst life, and the performance of playing stably for a long time be used to prepare acrylic acid catalyst.
R＝M/T (1)
In addition, method for producing acrylic acid of the present invention is a kind ofly to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation to prepare acrylic acid, it is characterized in that described preparation method is included in the operation of carrying out catalytic gas phase oxidation under the existence of catalyst of the present invention.According to method for producing acrylic acid of the present invention, can long-term stability and high productivity prepare acrylic acid.
The invention effect
Be used to prepare acrylic acid catalyst and method for producing acrylic acid according to of the present invention, just can utilizing molecular oxygen propane and/or methacrylaldehyde to be carried out when catalytic gas phase oxidation prepares acrylic acid, long-term stability and high productivity prepare acrylic acid.
The specific embodiment
Below, be used to prepare acrylic acid catalyst and used the method for producing acrylic acid of this catalyst to be elaborated of the present invention.But scope of the present invention is not subjected to the constraint of these explanations, except following illustrative, in the scope of not damaging aim of the present invention, can do suitable change and implement.
It is of the present invention that to be used to prepare acrylic acid catalyst be a kind ofly to be used to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation to prepare acrylic acid catalyst.As the acrylic acid unstripped gas of preparation, when containing molecular oxygen-containing gas, also contain propane and/or methacrylaldehyde at least.As molecular oxygen-containing gas, just be not particularly limited as long as contain molecular oxygen, for example, can use the gas of only forming by molecular oxygen, also can use air.
It is the catalyst activity composition of necessary composition that catalyst of the present invention contains with molybdenum and vanadium, when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the catalyst activity composition more than 2 θ=5 ° the degree of crystallinity T in 90 ° of following scopes in 20% following scope more than 5%.Above-mentioned degree of crystallinity T is preferably more than 7%, below 15%.Catalyst activity composition by will be when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure degree of crystallinity T in 90 ° of following scopes more than 2 θ=5 ° is controlled at more than 5% in the 20% following scope, catalyst of the present invention will have catalyst performance and outstanding catalyst lifes such as outstanding catalyst activity, selectivity, and has stability for a long time.Though its reason it be unclear that, when degree of crystallinity T less than 5%, it is just low that catalyst begins the acrylic acid selection rate from initial reaction stage; And when degree of crystallinity T surpassed 20%, it is just low that catalyst not only begins the acrylic acid selection rate from initial reaction stage, and catalyst life is short, causes in early days that easily performance is low by the time.
Degree of crystallinity among the present invention can be tried to achieve based on the method (absolute method) of JISK-0131 record by using the X-ray diffraction device.That is to say, as shown in the formula shown in (2) like that, try to achieve more than 2 θ=5 ° the X-ray diffraction intensity of the holocrystalline part in 90 ° of following scopes and more than 2 θ=5 ° all X-ray diffraction intensities in 90 ° of following scopes, calculate degree of crystallinity T by the X-ray diffraction intensity of holocrystalline part with respect to the ratio of all X-ray diffraction intensities then.In addition, all X-ray diffraction intensities are meant more than 2 θ=5 ° the integrated intensity of the X-ray diffraction in 90 ° of following scopes, and the X-ray diffraction intensity of holocrystalline part is meant more than 2 θ=5 ° the integrated intensity of the X-ray diffraction of the crystallinity part in 90 ° of following scopes.
T=(X-ray diffraction intensity of holocrystalline part)/(all X-ray diffraction intensities) * 100 (2)
Degree of crystallinity T specifically asks method as follows.After from the diffracting spectrum that X-ray diffraction analysis obtains, removing background, separate halo pattern (the Japanese original text: Ha ロ one バ タ one Application), then the crystallinity diffracted ray partly that obtains is separated by each peak that belongs to the noncrystalline part.Calculating belongs to integrated intensity (Sn) and the integrated intensity (Sc1, Sc2, Sc3...) at each peak of crystallinity part, the X-ray diffraction intensity Sc that calculates the holocrystalline part from the integrated intensity summation (Sc1+Sc2+Sc3+...) at each peak of crystallinity part then of the halo pattern of noncrystalline part.Degree of crystallinity T is tried to achieve by T=Sc/ (Sn+Sc) * 100.
Catalyst of the present invention is preferably: as shown in the formula shown in (1) like that, when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the degree of crystallinity ratio R that is calculated with respect to the ratio of above-mentioned degree of crystallinity T at the degree of crystallinity M at ° peak value place, 2 θ=22.2 ± 0.5 by the catalyst activity composition is in 0.30 following scope more than 0.06.Degree of crystallinity ratio R is more preferably in 0.25 following scope more than 0.07.
R＝M/T (1)
In following formula (1), M represents when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the degree of crystallinity at catalyst activity composition ° peak value place in 2 θ=22.2 ± 0.5.M can try to achieve based on the method (absolute method) of JISK-0131 record by using the X-ray diffraction device.That is to say, as shown in the formula shown in (3) like that, try to achieve the X-ray diffraction intensity of the crystallinity part of ° locating to have the peak in 2 θ=22.2 ± 0.5 and more than 2 θ=5 ° all X-ray diffraction intensities in 90 ° of following scopes, calculate M by the X-ray diffraction intensity of 2 θ=22.2 ± 0.5 ° with respect to the ratio of all X-ray diffraction intensities then.In addition, the X-ray diffraction intensity of ° locating to have the crystallinity part at peak in 2 θ=22.2 ± 0.5 is meant in 2 θ=22.2 ± 0.5 integrated intensity of the X-ray diffraction of ° locating to have the peak.
M=(X-ray diffraction intensity of peak crystallinity part)/(all X-ray diffraction intensities) * 100 (3)
The crystallinity of ° locating to have the peak in 2 θ=22.2 ± 0.5 partly is considered to belong to propane and/or methacrylaldehyde are carried out the reactive compound that catalytic gas phase oxidation prepares effective molybdenum of acrylic acid reaction and vanadium.Degree of crystallinity ratio R is equivalent to ° to locate to have in 2 θ=22.2 ± 0.5 X-ray diffraction intensity of crystallinity part at peak with respect to the ratio of the X-ray diffraction intensity of the holocrystalline part in 90 ° of following scopes more than 2 θ=5 °.That is to say, by regulation degree of crystallinity ratio R, just stipulated the ratio that specific crystallinity part is occupied in the holocrystalline part, thus can easily obtain having more outstanding catalyst performance and catalyst life, and the performance of playing stably for a long time be used to prepare acrylic acid catalyst.
Of the present invention be used to prepare acrylic acid catalyst contain with molybdenum and vanadium serve as must composition the catalyst activity composition.It is very important that the degree of crystallinity T that is used to prepare acrylic acid catalyst of the present invention satisfies above-mentioned scope.The present invention is applicable to following catalyst: it is the catalyst activity composition of necessary composition that this catalyst contains with molybdenum and vanadium.About serving as the catalyst of necessary composition with molybdenum and vanadium, there are various proposals in each company to the composition and the modulator approach of catalyst activity composition, but in the present invention, the composition of catalyst activity composition is preferably used the catalyst of following formula (4) expression.If the catalyst activity composition that contains in the catalyst has the composition with following formula (4) expression,, just can easily obtain having the catalyst of catalyst performances such as outstanding activity, acrylic acid yield and catalyst life by degree of crystallinity T is adjusted to proper range.
Mo
aV
bA
cB
dC
eD
fO
z (4)
Herein, Mo represents molybdenum, V represents vanadium, A represents niobium and/or tungsten, B represents to be selected from least a kind of element in chromium, manganese, iron, cobalt, nickel, copper, zinc and the bismuth, C represents to be selected from least a kind of element in tin, antimony, the tellurium, D represents to be selected from least a kind of element in titanium, aluminium, silicon and the zirconium, O represents oxygen, a, b, c, d, e, f and z represent the atomic ratio of Mo, V, A, B, C, D and O respectively, when a=12,1≤b≤14,0≤c≤12,0≤d≤10,0≤e≤6,0≤f≤40, z is the numerical value of being decided by the state of oxidation of each element.
Except serving as the catalyst activity composition of necessary composition with molybdenum and vanadium, catalyst of the present invention also can contain the inert carrier that is useful on the supported catalyst active component.As inert carrier, can use aluminium oxide, silica, silica-alumina, titanium oxide, magnesia, saponite, cordierite, silica-magnesia, carborundum, silicon nitride, zeolite etc.Support shapes is not particularly limited, can uses the carrier of shapes such as spherical, cylindric, ring-type.
Below, the modulator approach of catalyst of the present invention is described.Modulator approach to catalyst also has various proposals, for example can adopt following method.
Raw material as the catalyst activity composition, can obtain by following method: will constitute each element of catalyst activity composition salts such as oxide, hydroxide, ammonium salt, nitrate, carbonate, sulfate or acylate, these materials the aqueous solution, colloidal solution or contain the compound etc. of multiple element, for example be mixed into and make the aqueous solution or water-soluble serous (below be called " initiation material mixed liquor ") in the water.
The initiation material mixed liquor that obtains is carried out drying by methods such as heating or decompressions as required obtain catalyst precarsor.As carry out dry method by heating, for example can use spray dryer, drum dryer etc., its result can obtain pulverous catalyst precarsor.Also can use box drying machine, tunnel type drying machine etc. in air-flow, to heat the initiation material mixed liquor, obtain the catalyst precarsor of bulk or sheet.In addition, also can adopt earlier the initiation material mixed liquor to be concentrated and evaporation drying curing obtains the pie solid content, and then this pie solid content is carried out above-mentioned methods of heating treatment.As carry out dry method by decompression, for example can use vacuum drier to obtain block or pulverous catalyst precarsor.
The catalyst precarsor that obtains is passed through the powder that pulverizing process and classification operation etc. obtain suitable granularity as required, send in the forming process then.According to circumstances, send in the forming process again after also can earlier catalyst precarsor being calcined.Though the granularity of sending into the catalyst precarsor before the forming process is not particularly limited, from the good this point of mouldability, preferred granularity is that its particle by mesh 500 μ m sieve partly is more than the 90 quality %.
In forming process, can and beat sheet forming process etc. by extruding formation method and catalyst precarsor is configured as definite shape obtains formed body.Perhaps also can obtain load (load method) on any inert carrier with definite shape with being carried on as the initiation material mixed liquor of catalyst activity composition or catalyst precarsor.
To by extruding formation method or the shape of beating the formed body that sheet forming process etc. obtains be not particularly limited, can be spherical, cylindric, ring-type, any shape such as unsetting.Under spherical situation, there is no need certainly and must be essentially spherical getting final product for just spherical, cylindric and ring-type is too.
As the load method, for example can adopt evaporation drying solidification method and comminution granulation etc.Described evaporation drying solidification method be meant moist initiation material mixed liquor but with the original aqueous solution or water-soluble serous state on one side to its heating on one side with its coating or be attached on the inert carrier with definite shape, make it be carried on method on the inert carrier by drying afterwards.Described comminution granulation is meant the method that catalyst precarsor is carried on inert carrier with powder shaped.Wherein, especially preferably used the centrifugal flow of putting down in writing in the Japanese kokai publication sho 63-200839 communique to coat the comminution granulation of the swing mixing method of putting down in writing in method and the TOHKEMY 2004-136267 communique.The material of the inert carrier that can use in the load method and shape are as previously mentioned.
In forming process, the pore that also can use the shaping assistant and the adhesive that are used for improving formability, is used for forming at catalyst appropriate pore forms agent etc.Object lesson can be listed below: organic compounds such as ethylene glycol, glycerine, propionic acid, maleic acid, benzylalcohol, propyl alcohol, butanols and phenol; Water; Inorganic salts such as nitric acid, ammonium nitrate, ammonium carbonate etc.
In addition, in order to improve the mechanical strength of catalyst, also can use reinforcing agents such as silica, aluminium oxide, glass fibre, carborundum, silicon nitride.Reinforcing agent can make an addition in the initiation material mixed liquor, also can be matched with in the catalyst precarsor.
Formed body that obtains in forming process or load are admitted in the calcination process to be calcined.Calcining heat is preferably 350 ℃～450 ℃ scope, more preferably 380 ℃～420 ℃ scope.Calcination time is preferably 1 hour～and 10 hours.The calcining furnace that uses in calcination process is not particularly limited, can uses the box calcining furnace of general use or tunnel type calcining furnace etc.
Catalyst of the present invention has specific degree of crystallinity T, also preferably has specific degree of crystallinity ratio R, in order to obtain such catalyst, preferably adopts in the following method.That is to say, in the modulator approach of above-mentioned catalyst, can be when modulation initiation material mixed liquor, the mixeding liquid temperature when gradation drops into raw material or regulates raw material making time and mixed material; Perhaps under given conditions the catalyst after the calcining is carried out hydrothermal treatment consists.Particularly, when modulation initiation material mixed liquor, can be with the above at twice input of raw materials such as molybdenum, perhaps in the aqueous solution that contains molybdenum and vanadium (A liquid), add when the aqueous solution (B liquid) that contains B composition in the following formula (4), can last 30 seconds～10 minutes, preferably last 1 minute～5 minutes adding B liquid.Mixeding liquid temperature when the mixed material can suitably be set according to the raw material that drops into.When carrying out hydrothermal treatment consists under given conditions, in the autoclave of catalyst after the calcining and the moisture that will become saturated steam can being packed into simultaneously, add to depress in 150 ℃～250 ℃ of temperature, more preferably 190 ℃～240 ℃ scope and handled 2 hours～48 hours.In addition, in said method, the composition ratio by molybdenum and vanadium in the suitable adjustment catalyst activity composition also can change degree of crystallinity ratio R.
Next will describe method for producing acrylic acid of the present invention.Method for producing acrylic acid of the present invention is a kind ofly to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation to prepare acrylic acid, it is characterized in that described preparation method is included in the operation of carrying out catalytic gas phase oxidation under the existence of catalyst of the present invention.According to method for producing acrylic acid of the present invention, can long-term stability and high productivity prepare acrylic acid.
Method for producing acrylic acid of the present invention is as long as use catalyst of the present invention to carry out gas phase catalytic oxidation reaction, and the reactor of its use just is not particularly limited.As reactor, can use any in fixed bed reactors, flowing bed reactor, the moving-burden bed reactor.The preferred reactor that uses is fixed bed reactors.
As fixed bed reactors, preferred tubular reactor, more preferably multi-tubular reactor.Under this kind situation, fixed bed reactors have the reaction tube more than 1 or 2, are filled with catalyst in reaction tube.Reaction tube generally is disposed at vertical direction in fixed bed reactors.Tube inner diameter needs only and can just be not particularly limited by catalyst filling, but is generally 15～50mm, and more preferably 20～24mm is preferably 22～38mm especially.
The catalyst of filling in the reaction tube can be single catalyst, also can be the catalyst more than 2 kinds.The catalyst of filling in the reaction tube preferably is filled in on tube axial direction the catalyst layer in the reaction tube being divided in a plurality of reaction zones that are provided with more than 2 layers, and the degree of crystallinity ratio R of the catalyst of filling in each reaction zone is different.That is to say that reaction tube is preferably has a plurality of reaction zones of cutting apart on tube axial direction, be filled with the mutually different catalyst of degree of crystallinity ratio R in each reaction zone.More preferably, from the entrance side of the unstripped gas that contains propane and/or methacrylaldehyde and molecular oxygen-containing gas to outlet side, the mode catalyst filling in reaction tube that diminishes successively with the degree of crystallinity ratio R of a plurality of reaction zones.At this moment, the degree of crystallinity ratio R of the catalyst of filling in any one reaction zone is also preferably in 0.06～0.30 scope.In addition, in the fill method of above-mentioned catalyst, can be used in combination following method: with method of occupying method that mode that volume diminishes to outlet side gradually by the entrance side of unstripped gas fills, a part of catalyst being diluted with inert carrier etc. of catalyst etc.
The reaction zone number can be determined according to the scale of reaction condition and reactor.Because problems such as catalyst padding is numerous and diverse too much will take place the reaction zone number, therefore be preferably about 2～6 at industrial reaction zone number.
Reaction condition to acrylic acid preparation method of the present invention is not particularly limited, and the general condition of using in this kind reaction all can be implemented.For example, as unstripped gas, can use the gaseous mixture by following gas composition: the molecular oxygen of the propane of 1～15 capacity % (being preferably 4～12 capacity %) and/or methacrylaldehyde, 0.5～25 capacity % (being preferably 2～20 capacity %), the steam of 0～30 capacity % (being preferably 0～25 capacity %), all the other are inert gases such as nitrogen.Afterwards, can be in 200～400 ℃ temperature range, under the pressure of 0.1～1.0MPa, with 300～5,000h
-1(STP) space velocity contacts above-mentioned raw materials gas with catalyst.As reaction gas, not only can use the gaseous mixture of forming by propane and/or methacrylaldehyde, molecular oxygen and inert gas, also can use the gaseous mixture that contains methacrylaldehyde that obtains by the dehydration of glycerine and the oxidation reaction of propylene etc.In addition, in these gaseous mixtures, also can add air or oxygen etc. as required.
Embodiment
Below by enumerating embodiment the present invention is specifically described, but the present invention is not subjected to any restriction of following embodiment, implements after can doing suitably to change in meeting the scope of aim of the present invention, these all are included in the technical scope of invention.In addition, below for convenience, sometimes " mass parts " only remembered work " part ".
Acrolein conversion rate and acrylic acid yield are tried to achieve by following formula.
Acrolein conversion rate (mole %)=(the methacrylaldehyde molal quantity of reaction)/(the methacrylaldehyde molal quantity of supply) * 100
Acrylic acid yield (mole %)=(the acrylic acid molal quantity of generation)/(the methacrylaldehyde molal quantity of supply) * 100
Use the X ' PertPro of ス ペ Network ト リ ス Co., Ltd. system to carry out X-ray diffraction mensuration.The sample that is used for X-ray diffraction mensuration is prepared as follows: the catalyst activity composition being sieved separately, get about 0.5g from the powder by mesh 150 μ m, is the sheet of diameter 16mm, thickness 2mm with its compression forming.Use the Cu-K alpha ray, at X ray power output 40mA, 45kV, x-ray bombardment width 15mm, measure under the condition of 25 ℃ of temperature, more than 2 θ=5 °, measure the X-ray diffraction intensity of sample and measure being used for X-ray diffraction in 90 ° of following scopes.From the X ray diffracting spectrum that obtains, calculate degree of crystallinity T and degree of crystallinity ratio R based on the method (absolute method) of JISK0131 record.
(1) experimental example 1
(1-1) modulation of catalyst
3500 parts of distilled water are remained on 80 ℃ and under agitation to wherein adding 400 parts of ammonium paramolybdates, 116 parts of ammonium metavanadates and 76.5 parts of ammonium paratungstates (A liquid).In addition, 400 parts of distilled water are remained on 80 ℃ also under agitation to wherein dissolving 143 parts of copper nitrates (B liquid).In A liquid, last 2 minutes interpolation B liquid while stirring A liquid, obtain mixed liquor.In the mixed liquor that obtains, further add 24.1 parts of antimony trioxides, stir and obtained suspension in 1 hour.In the suspension that obtains, add 100 parts of ammonium paramolybdates again, further stir and obtained the initiation material mixed liquor in 1 hour.With drum dryer this initiation material mixed liquor is carried out drying, obtain the graininess powder.With the graininess powder that obtains under air atmosphere about 2 hours of 210 ℃ of dryings.Dried graininess powder is crushed to below the 250 μ m, obtains the catalyst precarsor of powder shaped.In the centrifugal flow coating unit, drop into the silica-alumina ball type carrier of 1500 parts of average grain diameter 4.5mm, feed 90 ℃ of hot blasts then on one side, drop into aqueous ammonium nitrate solution and catalyst precarsor on one side simultaneously, catalyst precarsor is carried on the carrier as 15 quality % of adhesive.Next, under air atmosphere,, obtain catalyst 1 390 ℃ of calcinings 6 hours.The load factor of catalyst 1 is about 30 quality %, and the metallic element that removes behind the deoxidation is composed as follows.
Catalyst 1:Mo
12V
4.2Cu
2.5W
1.2Sb
0.7
Load factor is tried to achieve from following formula.
The carrier quality (g) * 100 of load factor (quality %)=(the carrier quality (g) of catalyst quality (g)-use)/use
When measuring by X-ray diffraction, the catalyst activity composition of catalyst 1 degree of crystallinity T in 90 ° of following scopes more than 2 θ=5 ° is 7.7%, and the degree of crystallinity ratio R of catalyst 1 is 0.14.
(1-2) reaction
Ready reaction device on vertical direction, this reactor is made up of the SUS of total length 3000mm, internal diameter 25mm system reaction tube and the circulate shell of thermal medium of being used to that covers this reaction tube.Cast catalyst 1 from reaction tube top and fill, make layer reach 2900mm.Heat medium temperature (reaction temperature) is remained on 263 ℃, importing by methacrylaldehyde 7 capacity %, oxygen 8.5 capacity %, steam 10 capacity %, remainder from the reaction tube bottom of having filled catalyst with space velocity 1650hr-1 (STP) is the gaseous mixture that inert gas such as nitrogen is formed, and carries out the oxidation reaction of methacrylaldehyde.The result of acrolein conversion rate and acrylic acid yield is as shown in table 1.In addition, suitably will react continuation 8000 hours in the reacting condition temperature, its result is also as shown in table 1.In experimental example 1, the acrylic acid yield at initial stage is more than the 95.0mol%, has shown high value, and after through 8000 hours, acrylic acid yield has also only reduced 0.3mol%.In experimental example 1, can long-term stability and high productivity prepare acrylic acid.
(2) experimental example 2
Except the amount of the ammonium paramolybdate that will add in A liquid and suspension becomes 500 parts, 0 part respectively, and the time of adding B liquid in A liquid was become outside 1 minute, similarly modulated catalyst, obtain catalyst 2 with experimental example 1.The load factor of this catalyst 2 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 1.The degree of crystallinity T of catalyst 2 is 10.5%, and degree of crystallinity ratio R is 0.10.
Similarly the catalyst 2 that obtains is filled with experimental example 1, under similarity condition, carry out the oxidation reaction of methacrylaldehyde.The result is as shown in table 1.In experimental example 2, the acrylic acid yield at initial stage also is more than the 95.0mol%, to have shown high value.
(3) experimental example 3
Except the maintenance temperature with A liquid and B liquid becomes 90 ℃, and the time of adding B liquid in A liquid become 10 seconds with outside interior, similarly modulated catalyst, obtain catalyst 3 with experimental example 2.The load factor of this catalyst 3 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 2.The degree of crystallinity T of catalyst 3 is 20.8%, and degree of crystallinity ratio R is 0.04.
Similarly the catalyst 3 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In addition, suitably will react continuation 8000 hours in the reacting condition temperature, its result is also as shown in table 1.In experimental example 3,,, lower so the acrylic acid yield at initial stage is 92.8mol% because the degree of crystallinity T of catalyst 3 has surpassed 20%.After through 8000 hours, acrylic acid yield further descends, with the preliminary phase ratio 2.4mol% that descended.
(4) experimental example 4
Except the maintenance temperature with A liquid and B liquid becomes 70 ℃, the amount of the ammonium paramolybdate that adds in A liquid and suspension is become 100 parts, 400 parts respectively, with the quantitative change of ammonium metavanadate is 138 parts, and the time of adding B liquid in A liquid become outside 12 minutes, similarly modulate catalyst with experimental example 1, obtained catalyst 4.The load factor of this catalyst 4 is about 30 quality %, and the metallic element that removes behind the deoxidation is composed as follows.
Catalyst 4:Mo
12V
5Cu
2.5W
1.2Sb
0.7
The degree of crystallinity T of catalyst 4 is 5.5%, and degree of crystallinity ratio R is 0.31.
Similarly the catalyst 4 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In addition, suitably will react continuation 8000 hours in the reacting condition temperature, its result is also as shown in table 1.In experimental example 4, because the degree of crystallinity T of catalyst 4 is 5.5% low slightly, degree of crystallinity ratio R 0.31 is high value, so acrylic acid yield is low than experimental example 1,2, be 94.2mol% in the early stage, is 93.7mol% after 8000 hours.
(5) experimental example 5
Except the maintenance temperature with A liquid and B liquid becomes 80 ℃, the amount of the ammonium paramolybdate that adds in A liquid and suspension is become 0 part, 500 parts respectively, and the time of adding B liquid in A liquid become outside 20 minutes, similarly modulated catalyst with experimental example 4, obtain catalyst 5.The load factor of this catalyst 5 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 4.The degree of crystallinity T of catalyst 5 is 4.7%, and degree of crystallinity ratio R is 0.35.
Similarly the catalyst 5 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In addition, suitably will react continuation 8000 hours in the reacting condition temperature, its result is also as shown in table 1.In experimental example 5,,, lower so the acrylic acid yield at initial stage is 92.5mol% because the degree of crystallinity T of catalyst 5 is lower than 5.0%.After through 8000 hours, acrylic acid yield further descends, with the preliminary phase ratio 1.6mol% that descended.
(6) experimental example 6
Except the maintenance temperature with A liquid and B liquid becomes 90 ℃, the amount of the ammonium paramolybdate that adds in A liquid and suspension is become 450 parts, 50 parts respectively, with the quantitative change of ammonium metavanadate is 82.8 parts, with the quantitative change of copper nitrate is 228 parts, and in A liquid, add when the B liquid B liquid added quickly outside, similarly modulate catalyst with experimental example 1, obtained catalyst 6.The load factor of this catalyst 6 is about 30 quality %, and the metallic element that removes behind the deoxidation is composed as follows.
Catalyst 6:Mo
12V
3Cu
4W
1.2Sb
0.7
The degree of crystallinity T of catalyst 6 is 19.1%, and degree of crystallinity ratio R is 0.05.
Similarly the catalyst 6 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 6, because the degree of crystallinity T of catalyst 6 is 19.1% high slightly, degree of crystallinity ratio R is 0.05 lower, so the acrylic acid yield at initial stage is low than experimental example 1,2, is 94.2mol%.
(7) experimental example 7
Except the maintenance temperature with A liquid and B liquid becomes 80 ℃, and the amount of the ammonium paramolybdate that adds in A liquid and suspension become respectively outside 0 part, 500 parts, similarly modulated catalyst, obtain catalyst 7 with experimental example 6.The load factor of this catalyst 7 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 6.The degree of crystallinity T of catalyst 7 is 4.6%, and degree of crystallinity ratio R is 0.05.
Similarly the catalyst 7 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 7,,, lower so the acrylic acid yield at initial stage is 92.6mol% because the degree of crystallinity T of catalyst 7 is lower than 5.0%.
(8) experimental example 8
Except the quantitative change with ammonium metavanadate is that 110 parts, the quantitative change of copper nitrate are that 200 parts, the quantitative change of antimony trioxide are 34.4 parts, and the time of adding B liquid in A liquid was become outside 30 seconds, similarly modulated catalyst, obtain catalyst 8 with experimental example 1.The load factor of this catalyst 8 is about 32 quality %, and the metallic element that removes behind the deoxidation is composed as follows.
Catalyst 8:Mo
12V
4Cu
3.5W
1.2Sb
1
The degree of crystallinity T of catalyst 8 is 13.2%, and degree of crystallinity ratio R is 0.08.
Similarly the catalyst 8 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 8, the acrylic acid yield at initial stage is more than the 95.0mol%, has shown high value.
(9) experimental example 9
Except the maintenance temperature with A liquid and B liquid becomes 70 ℃, the amount of the ammonium paramolybdate that adds in A liquid and suspension is become 300 parts, 200 parts respectively, with the quantitative change of ammonium metavanadate is that 138 parts, the quantitative change of copper nitrate are that 171 parts, the quantitative change of antimony trioxide are 34.4 parts, and the time of adding B liquid in A liquid become outside 5 minutes, similarly modulate catalyst with experimental example 1, obtained catalyst 9.The load factor of this catalyst 9 is about 32 quality %, and the metallic element that removes behind the deoxidation is composed as follows.
Catalyst 9:Mo
12V
5Cu
3W
1.2Sb
1
The degree of crystallinity T of catalyst 9 is 7.2%, and degree of crystallinity ratio R is 0.24.
Similarly the catalyst 9 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 9, the acrylic acid yield at initial stage is more than the 95.0mol%, has shown high value.
(10) experimental example 10
Except the amount of the ammonium paramolybdate that will add in A liquid and suspension becomes 150 parts, 350 parts respectively, and the time of adding B liquid in A liquid was become outside 8 minutes, similarly modulated catalyst, obtain catalyst 10 with experimental example 9.The load factor of this catalyst 10 is about 32 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 9.The degree of crystallinity T of catalyst 10 is 6.4%, and degree of crystallinity ratio R is 0.29.
Similarly the catalyst 10 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 10, the acrylic acid yield at initial stage is 94.4mol%, has shown than higher value.
(11) experimental example 11
Except the maintenance temperature with A liquid and B liquid becomes 90 ℃, the amount of the ammonium paramolybdate that adds in A liquid and suspension is become 350 parts, 150 parts respectively, with the quantitative change of ammonium metavanadate is that 82.8 parts, the quantitative change of copper nitrate are that 228 parts, the quantitative change of antimony trioxide are 34.4 parts, and the time of adding B liquid in A liquid become outside 30 seconds, similarly modulate catalyst with experimental example 1, obtained catalyst 11.The load factor of this catalyst 11 is about 31 quality %, and the metallic element that removes behind the deoxidation is composed as follows.Catalyst 11:Mo
12V
3Cu
4W
1.2Sb
1
The degree of crystallinity T of catalyst 11 is 15.9%, and degree of crystallinity ratio R is 0.07.
Similarly the catalyst 11 that obtains is filled with experimental example 1, under similarity condition, carry out the acrolein oxidation reaction.The result is as shown in table 1.In experimental example 11, the acrylic acid yield at initial stage is 94.8mol%, has shown than higher value.
[table 1]
(12) experimental example 12
(12-1) modulation of catalyst
Except the average grain diameter of the silica-alumina spheroid carrier that will use in experimental example 1 becomes 7.5mm, similarly modulated catalyst with experimental example 1, obtain catalyst 12.The load factor of this catalyst 12 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 1.Degree of crystallinity T is identical with catalyst 1 with degree of crystallinity ratio R.
(12-2) reaction
Ready reaction device on vertical direction, this reactor is made up of the SUS of total length 3000mm, internal diameter 25mm system reaction tube and the circulate shell of thermal medium of being used to that covers this reaction tube.Cast catalyst 12 successively from reaction tube top, catalyst 2 is filled, and makes that the long layer for 900mm, catalyst 2 of layer of catalyst 12 is long to be 2000mm.
Heat medium temperature (reaction temperature) is remained on 263 ℃, importing by methacrylaldehyde 8.5 capacity %, oxygen 10.2 capacity %, steam 8 capacity %, remainder from the reaction tube bottom of having filled catalyst with space velocity 1700hr-1 (STP) is the gaseous mixture that inert gas such as nitrogen is formed, and carries out the oxidation reaction of methacrylaldehyde.In experimental example 12, with respect to the flow direction of gaseous mixture, catalyst 12 is disposed at the entrance side of reaction tube, and catalyst 2 is disposed at the outlet side of reaction tube.Suitably will react continuation 8000 hours in the reacting condition temperature.The result is as shown in table 2.In experimental example 12, with the 2 kind catalyst of degree of crystallinity ratio R in 0.06～0.30 scope, be that catalyst 2 and catalyst 12 are packed into reaction tube, and disposed the high catalyst 12 of degree of crystallinity ratio R, disposed the low catalyst 2 of degree of crystallinity ratio R at outlet side at entrance side.Its result in the early stage with through after 8000 hours, has all obtained the above acrylic acid high yield of 95.0mol%.
(13) experimental example 13
Except the average grain diameter of the silica-alumina spheroid carrier that will use in experimental example 2 becomes 7.5mm, similarly modulated catalyst with experimental example 2, obtain catalyst 13.The load factor of this catalyst 13 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 2.Degree of crystallinity T is identical with catalyst 2 with degree of crystallinity ratio R.
With the same reaction tube of experimental example 12 in, cast catalyst 13 successively from reaction tube top, catalyst 1 is filled, make that the long layer for 900mm, catalyst 1 of layer of catalyst 13 is long to be 2000mm, and with experimental example 12 similarity conditions under carry out the oxidation reaction of methacrylaldehyde.In experimental example 13, with respect to the flow direction of gaseous mixture, catalyst 13 is disposed at the entrance side of reaction tube, and catalyst 1 is disposed at the outlet side of reaction tube.The result is as shown in table 2.In experimental example 13, with the 2 kind catalyst of degree of crystallinity ratio R in 0.06～0.30 scope, be that catalyst 1 and catalyst 13 are packed into reaction tube, and disposed the low catalyst 13 of degree of crystallinity ratio R, disposed the high catalyst 1 of degree of crystallinity ratio R at outlet side at entrance side.In experimental example 13,, compare performance with experimental example 12 and descend though all kept high acrylic acid yield in the early stage and after 8000 hours.
(14) experimental example 14
Except the average grain diameter of the silica-alumina spheroid carrier that will use in experimental example 3 becomes 7.5mm, similarly modulated catalyst with experimental example 3, obtain catalyst 14.The load factor of this catalyst 14 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 3.Degree of crystallinity T is also identical with catalyst 3 with degree of crystallinity ratio R.
With the same reaction tube of experimental example 12 in, cast catalyst 14 successively from reaction tube top, catalyst 3 is filled, make that the long layer for 900mm, catalyst 3 of layer of catalyst 14 is long to be 2000mm, and with experimental example 12 similarity conditions under carry out the oxidation reaction of methacrylaldehyde.In experimental example 14, with respect to the flow direction of gaseous mixture, catalyst 14 is disposed at the entrance side of reaction tube, and catalyst 3 is disposed at the outlet side of reaction tube.The result is as shown in table 2.In experimental example 14, with degree of crystallinity ratio R outside 0.06～0.30 scope and catalyst 3 and catalyst 14 with identical degree of crystallinity ratio R be packed into reaction tube.In experimental example 14, acrylic acid yield is compared with experimental example 12,13 and is descended.
(15) experimental example 15
Except the average grain diameter of the silica-alumina spheroid carrier that will use in experimental example 5 becomes 7.5mm, similarly modulated catalyst with experimental example 5, obtain catalyst 15.The load factor of this catalyst 15 is about 30 quality %, except that the metallic element behind the deoxidation is formed identical with catalyst 5.Degree of crystallinity T is also identical with catalyst 5 with degree of crystallinity ratio R.
With the same reaction tube of experimental example 12 in, cast catalyst 15 successively from reaction tube top, catalyst 3 is filled, make that the long layer for 900mm, catalyst 3 of layer of catalyst 15 is long to be 2000mm, and with experimental example 12 similarity conditions under carry out the oxidation reaction of methacrylaldehyde.In experimental example 15, with respect to the flow direction of gaseous mixture, catalyst 15 is disposed at the entrance side of reaction tube, and catalyst 3 is disposed at the outlet side of reaction tube.The result is as shown in table 2.In experimental example 15, with degree of crystallinity ratio R at 0.06～0.30 extraneous 2 kinds of catalyst, be that catalyst 3 and catalyst 15 are packed into reaction tube, and disposed the high catalyst 15 of degree of crystallinity ratio R, disposed the low catalyst 3 of degree of crystallinity ratio R at outlet side at entrance side.In experimental example 15, acrylic acid yield is compared with experimental example 12,13 decline has been taken place.
[table 2]
Claims (7)
1. one kind is used to prepare acrylic acid catalyst, and described catalyst is to be used to utilize molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation prepare acrylic acid catalyst, it is characterized in that,
It is the catalyst activity composition of necessary composition that described catalyst contains with molybdenum and vanadium,
When having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the catalyst activity composition more than 2 θ=5 ° the degree of crystallinity T in 90 ° of following scopes in 20% following scope more than 5%.
2. according to claim 1ly be used to prepare acrylic acid catalyst, wherein, with the degree of crystallinity ratio R of following formula (1) expression in 0.30 following scope more than 0.06,
R＝M/T (1)
M represents when having used the Alpha-ray X-ray diffraction analysis of Cu-K to measure, the degree of crystallinity at catalyst activity composition ° peak value place in 2 θ=22.2 ± 0.5.
3. according to claim 1 and 2ly be used to prepare acrylic acid catalyst, wherein, described catalyst also contains the inert carrier that is useful on the described catalyst activity composition of load.
4. method for producing acrylic acid, described preparation method utilizes molecular oxygen-containing gas that propane and/or methacrylaldehyde are carried out catalytic gas phase oxidation to prepare acrylic acid, it is characterized in that,
Described preparation method is included in the operation of carrying out catalytic gas phase oxidation under the existence of any described catalyst among the claim 1-3.
5. method for producing acrylic acid according to claim 4 wherein, uses the fixed bed reactors with reaction tube, is filled with described catalyst in described reaction tube.
6. method for producing acrylic acid according to claim 5, wherein,
Described reaction tube has a plurality of reaction zones of cutting apart on tube axial direction,
In each reaction zone, be filled with the mutually different catalyst of described degree of crystallinity ratio R.
7. method for producing acrylic acid according to claim 6, wherein, to outlet side, the degree of crystallinity ratio R of described a plurality of reaction zones diminishes successively from the entrance side of the unstripped gas that contains propane and/or methacrylaldehyde and molecular oxygen-containing gas.
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| JP2015034154A (en) * | 2013-08-09 | 2015-02-19 | 日本化薬株式会社 | Filling method of catalyst for selectively abating propionic acid |
| BR112021000848B1 (en) * | 2018-07-19 | 2024-02-06 | Nova Chemicals (International) S.A. | CATALYST FOR OXIDATIVE DEHYDROGENATION, METHOD OF PREPARATION THEREOF AND METHOD FOR OXIDATIVE DEHYDROGENATION |
| EP4209268A4 (en) * | 2020-09-03 | 2024-09-18 | Nippon Shokubai Co., Ltd. | Catalyst for acrylic acid production, method for producing same, and method for producing acrylic acid |
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| DE10351269A1 (en) * | 2003-10-31 | 2005-06-02 | Basf Ag | Long-term operation of heterogeneously catalyzed gas phase partial oxidation of propene to acrylic acid, comprises interrupting gas phase partial oxidation before temperature increase of fixed catalyst bed is permanent |
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| JP4947917B2 (en) * | 2005-04-18 | 2012-06-06 | 株式会社日本触媒 | Fixed bed reactor for gas phase catalytic oxidation and method for producing acrolein or acrylic acid |
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-
2009
- 2009-09-25 US US12/999,789 patent/US20110166384A1/en not_active Abandoned
- 2009-09-25 CN CN2009801231284A patent/CN102066000A/en active Pending
- 2009-09-25 EP EP09817709.0A patent/EP2347823B1/en active Active
- 2009-09-25 JP JP2010531831A patent/JP5548132B2/en active Active
- 2009-09-25 WO PCT/JP2009/066655 patent/WO2010038676A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| US20110166384A1 (en) | 2011-07-07 |
| EP2347823A4 (en) | 2013-08-14 |
| JPWO2010038676A1 (en) | 2012-03-01 |
| EP2347823A1 (en) | 2011-07-27 |
| EP2347823B1 (en) | 2016-08-31 |
| WO2010038676A1 (en) | 2010-04-08 |
| JP5548132B2 (en) | 2014-07-16 |
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Application publication date: 20110518 |